Substituted O-(aminosulfonyl)-glycolic anilides

ABSTRACT

New and valuable substituted O-(aminosulfonyl)-glycolic anilides and a process for controlling the growth of unwanted plants with these compounds.

United States Patent Fischer et a]. Dec. 9, 1975 SUBSTITUTED O-(AMINOSULFONYL)-GLYCOLIC [52] US. Cl .r 260/456 A NI [5 1] Int. Cl. C07C 143/02 8 f 260 456 A; 71/103 [75] Inventors: Adolf Fischer, Mutterstaclt; Gerhard [5 1 new 0 Search Hamprecht, Mannheim; Dietrich Marigold, Neckargemuend; [56] References cued Wolfgang Rohr, Mannheim, all of UNITED STATES PATENTS Germany 3.53am 10/1970 Soong et al. 260/456 A [73] Assignee: Badische Anilin & Soda-Fabrik Aktiengesellschaft, Ludwigshafen Primary Examzner-I-loward T Mars (Rhine), Germany Assistant Examiner-Nicky Chan Attorney, Agent, or Firmlohnst0n, Keil, Thompson [22] Filed. Sept. 3, 1974 & Shurfleff [2]] Appl. No.1 502,746

Related us. Application Data ABSTRACT [62] Division ofSer. N0 3215481311. 5, 1973 Pm. N0, New n valuable substituted y l- 3,870740v glycolic anilides and a process for controlling the growth of unwanted plants with these compounds. [30] Foreign Application Priority Data Jan. [3, I972 Germany 2201432 6 Claims, N0 Drawings SUBSTITUTED -(AMlNOSULFONYL)-GLYCOLIC ANILIDES This is a division of application Ser. No. 321,548, filed Jan. 5, 1973, now US. Pat. No. 3,870,740.

The present invention relates to new and valuable substituted 0-[aminosulfonyl1-glycolic anilides, their preparation and use as herbicides.

It is known to use chloroacetic acid-N-isopropylanilide as a herbicide. However, its biological action is only moderate.

We have now found that substituted O-[aminosulfonyll-glycolic anilides of the formula n'uusopcrniu Alopecurus myosuroia'es slender foxtail Amaranrhur spp. amaranth species Avena farua wild oat Bromus spp. brome species Chenopodr'um spp. goosefoot species Dactylis glomeram orchardgrass Digilaria sanguinali: large crabgrass Echinochloa ems-gall! barnyardgrass Eleun'ne indr'ca goose ass gr Galium aparr'ne catchweed bedstraw Lamium spp. deadnettle species Lalium spp. ryegrass species Marrican'a chamomilla chamomile Panicium spp. panicum spp.

Poa spp. luegrass species Setaria spp. foxtail species Sinapt's arvensis wild mustard without causing damage to the crop plants:

Allium cepa onions Hera vulgaris beet Brassica spp. cabbage species Cucuml's sarivus cucumbers Daucus carora carrots Gossypium hirsurum cotton Helt'anthus annuus sunflower Hordeum vulgare barley Lacruca spp. lettuce species Linum usr'rarissimum flax Medicago sativa alfalfa Oryza sariva rice Pelrorelinum .rativum parsley Pisum sativum peas Phaseolus spp. beans Secale cereal: rye

Soja hispida (Glycine max.) soybeans Solarium luberosum potatoes Splnaci'a oleracea spinach Sorghum bicolor sorghum Triricum assrivum wheat Tnfolium spp. clover Zea mays Indian Corn Application rates are from 0.2 to 5 kg of active ingredient per hectare; the compounds may be applied before sowing, or before or after emergence of the plants.

The compounds of the invention may be prepared by reacting a substituted glycolic anilide with a substituted aminosulfonyl chloride in the presence of an acid acceptor, e.g., triethylamine and pyridine.

EXAMPLE 1 O[isopropylaminosulfonyll-glycolic acid-N-butynl -yl-3-anilide At 0 to 5C and while stirring, a solution of 333 parts by weight of isopropylaminosulfonyl chloride in parts by weight of dichloromethane was added to a solution of 35.5 parts by weight of glycolic acid-N-butynl-yl-3-anilide and 21.4 parts by weight of triethylamine in 600 parts by weight of dichloromethane. After 2 hours the reaction mixture was successively washed with dilute hydrochloric acid, water, sodium bicarbonate solution, and again with water, and then dried with magnesium sulfate. The crude product, melting at 99 to C, was obtained from the organic phase upon concentration in vacuo. The pure compound melting at 108 to 110C may be obtained by recrystallization from benzene.

1 The compound has the following structural formula:

CH-CH,

The compounds listed below may be obtained analogously:

The following compounds were obtained analogously:

glycolic acid-N-isopropylanilide, m.p. 59 to 60C glycolic acid-N-isobutylanilide, m.p. 53 to 54C glycolic acid-N-tert-butylanilide, m.p. 55 to 56C.

Glycolic anilides are obtained in the same manner by reacting, in accordance with the scheme shown below, N-alkylanilines with l,3-dioxolane-2,4-dione (J. Chem. Soc., 1357, I951). R and R have the meanings given Glycolic acid-N-methylanilide A solution of 10.7 parts by weight of N-methylaniline in 20 parts by weight of tetrahydrofuran has added to it, at to C and with stirring, a solution of 10.2 parts by weight of l,3-dioxolane-2,4-dione in parts by weight of tetrahydrofuran. The reaction mixture was then stirred at room temperature until no more carbon dioxide evolved, and subsequently concentrated to dryness in vacuo. The crude product obtained melts at 48 to 50C; the analytically pure compound is obtained by recrystallization from ether; m.p.: 50 to 52C.

The following compounds were obtained analogously:

glycolic acid-N-ethylanilide, m.p. 39 to 41C glycolic acid-N-n-propylanilide, m.p. 68 to 69C glycolic acidN-propargylanilide, m.p. 69 to 71C glycolic acid-N-3-methylbutyn-l-yl-3-anilide glycolic acid-N-allylanilide glycolic acid-N-buten-l-yl-3-anilide glycolic acid-N-3-methylbuten-1-yl-3-anilide glycolic acid-N-cyclohexylanilide glycolic acid-N-cyclopentylanilide glycolic acid-N-benzylanilide.

The agents according to the invention may be used as solutions, emulsions, suspensions or dusts. The form of application depends entirely on the purpose for which the agents are being used; in any case it should ensure a fine distribution of the active ingredient.

For the preparation of solutions to be sprayed direct, hydrocarbons having boiling points higher than 150C, e.g. tetrahydronaphthalene or alkylated naphthalenes, or organic liquids having boiling points higher than l50C and having one or more than one functional group, eg the keto group, the ether group, the ester group or the amide group, this group or these groups being attached as substituent(s) to a hydrocarbon chain or being a component of a hetero-cyclic ring, may be used as spray liquids.

Aqueous formulations may be prepared from emulsion concentrates, pastes or wettable powders by adding water. To prepare emulsions the ingredients as such or dissolved in a solvent may be homogenized in water or organic solvents by means of wetting or dispersing agents, e.g., polyethylene oxide adducts. Concentrates which are suitable for dilution with water may be prepared from active ingredient, emulsifying or dispersing agent and possibly solvent.

Dusts may be prepared by mixing or grinding the active ingredients with a solid carrier, e.g., kieselguhr, talc, clay or fertilizers.

Granules may be prepared by applying the active ingredients to solid carriers of various particle sizes.

Adherents, oils and other herbicidal active ingredients may also be added.

EXAMPLE 2 In the greenhouse, loamy sandy soil was filled into pots and sown with Zea mays, Soja hispida, Gossypium hirsutum, Beta vulgaris, Echinochloa crus-galli, Setaria spp., Poa trivialis, Bromus teclorum and Alopecurus myosuroides. The soil prepared in this manner was then treated with 2 kg per hectare of O-(isopropylaminosulfonyl)-glycolic acid-N-butyn-l-yl-3-anilide (I) and, for comparison, with 2 kg per hectare of chloroacetic acid- N-isopropylanilide (11), each active ingredient being dispersed in 500 liters of water per hectare.

After 4 to 5 weeks it was ascertained that active ingredient I had the same good crop plant compatibility as [1, combined with a stronger herbicidal action.

The results of this experiment are given below:

0 no damage 100 complete destruction EXAMPLE 3 0n an agricultural plot the plants Zea mays, Gossypium hirsutum, Scja hispida, Beta vulgaris, Echinochloa crus-galli, Digitaria sanguinalis, Pam'cum virgatum, Eleusine indica and Pan annua were treated at a growth height of 2 to 14 cm with 2 kg per hectare of l and 2 kg per hectare of [1, each active ingredient being emulsified in 500 liters of water per hectare.

After 3 to 4 weeks it was ascertained that active ingredient 1 had not only better crop plant compatibility than II, but also a stronger herbicidal action.

The results of this experiment are given below:

Active ingredient l1 Zea may: 0 0

Gossypium hirsutum 0 l5 Soja hispida 5 15 Beta vul an: 0 l0 Echinoc lua crus-galli 60 Digr'mria .ranguinah's 40 Panicum virgatum 90 40 Eleusine indl'ca 90 30 Pan annua 80 i5 0 no damage complete destruction The action of the following compounds corresponds to that of l above:

O-(isopropylaminosulfonyl)-glycolic acid-N- methylanilide O(isopropylaminosulfonyl )-glycolic acid-N- acid-N-sec- EXAMPLE 4 90 parts by weight of compound I is mixed with 10 parts by weight of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

EXAMPLE 5 20 parts by weight of compound I is dissolved in a mixture consisting of 80 parts by weight of xylene, parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 6 EXAMPLE 7 parts by weight of compound I is dissolved in a mixture consisting of parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

EXAMPLE 8 20 parts by weight of compound I is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquid is obtained containing 0.1% by weight of the active ingredient.

EXAMPLE 9 3 parts by weight of compound 1 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingrediem.

EXAMPLE 10 30 parts by weight of compound I is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

EXAMPLE 1 l acid-N- Vll ()-(isopropylaminosulfonyl)-glycolic acid-N- ethylanilide Vlll O-(ethylaminosulfonyl )-glycolic acid-N- ethylanilide After 3 weeks it was ascertained that the active ing redients exhibited good crop plant compatibility combined with an excellent herbicidal action.

The results are given below:

Active ingredient l Ill IV V VI Vll Vlll Crop plants:

Soja hispida 0 5 0 0 0 0 0 Gossypium hirsurum 0 0 0 0 0 0 0 Beta vulgaris 0 0 0 0 0 0 0 Brassica napus 0 0 0 0 0 0 0 Hell'anthu: annuus 0 0 0 0 0 0 0 Allium cepa 0 0 0 O 0 0 0 Spinacia olemcea 0 0 0 0 0 0 0 Pisum sativum 0 0 0 0 0 O 0 Unwanted plants;

Echinochloa crus-galli 95 I00 95 95 I00 mo 95 Digiraria sanguinalis 95 100 95 I00 90 Setaria faberii 95 95 90 I00 95 95 Pan annua I00 100 100 l00 l00 100 95 Lolium multiflorum I00 100 95 95 I00 l00 95 Eleusine indica I00 100 95 90 I00 95 90 Matricaria rhamumilla 80 90 80 80 90 80 75 0 no damage 100 complete destruction EXAMPLE 12 acid-N- Vll O-( isopropylaminosulfonyl)-glycolic acid-N- ethyl-anilide Vlll O-(ethylaminosulfonyl)-glycolic acid-N- ethylanilide.

After 3 weeks it was ascertained that the active ingredients exhibited favorable crop plant compatibility combined with a good herbicidal action.

The results are given below:

Active ingredient I III N V VI VII Vlll Crop plants:

Soja hispidn O 0 0 0 0 Beta vulgaris 0 0 0 0 0 0 0 Gossypium hirrutum 0 0 0 0 0 0 0 Oryzn saliva l0 5 5 l5 5 5 Trr'n'cum aeslr'vum l0 5 5 5 5 l0 5 Zea may: 0 0 0 0 0 5 0 Unwanted plants:

Alapecurus myosuror'de: 90 95 85 80 90 95 90 Lolium mulnjlorum 90 95 80 80 85 90 90 Setan'a faberr'i 95 I00 90 90 90 95 95 Eleusine indica B5 95 90 80 B5 90 90 Echinochloa crus-galli 75 95 90 90 80 80 85 Chenopodium album 80 90 70 70 70 80 75 Mam'caria chamomilln 80 90 75 75 70 80 80 0 no damage I00 complete destruction The action of the following compounds corresponds to that of the compounds examined in Examples 1 l and l2:

O-(aminosulfonyl)-glycolic acid N-butyn-1-yl-3-anilide O-(isopropylaminosulfonyl)-glycolic butylanilide O-(methylaminosulfonyl)-glycolic acid-N-methylanilide O-(ethylaminosulfonyl)-glycolic acid-N-tertacid-N-methylanilide O-(methylaminosulfonyl )-glyc0lic acid'N-npropylanilide O-( isopropylaminosulfonyl )-glycolic acid-N-npropylanilide O-(ethylarninosulfonyl )-glycolic acid-N-secbutylanilide O-( isopropylaminosulfonyl )-glycolic acid-N- ethylanilide O-(isopropylaminosulfonyl)-glycolic acid-N-propargylanilide O-(pentylaminosulfonyl)-glycolic acid-N-butynl -yl- 3-anilide O-(aminosulfonyl)-glycolic acid-N-methylanilide We claim:

1. A substituted O-(aminosulfonyl)-glycolic anilide of the formula where R denotes hydrogen or alkyl of one to six carbon atoms, R denotes phenyl, and R denotes alkenyl of three to six carbon atoms.

2. The compound of claim 1, which is O(isopropylaminosulfonyl)-glycolic acid-N-buten l -yl-3- anilide.

3. The compound of claim 1, which is O-(aminosulfonyl)-glycolic acid-N-butenl -yl-3-anilide.

4. The compound of claim 1, which is O-(methylaminosulfonyl)-glycolic acid-N-buten-l-yl-li-anilide.

5. The compound of claim 1, which is 0- (ethylaminosulfonyl)-glycolic acid-N-buten-l-yl-li-anilide.

6. The compound of claim 1, which is O- (propylaminosulfonyl )-glycolic acid-N-butenl -yl-3- anilide.

l I l 

1. A SUBSTITUTED O-(AMINOSULFONYL)-GLYCOLIC ANILIDE OF THE FORMULA
 2. The compound of claim 1, which is O-(isopropylaminosulfonyl)-glycolic acid-N-buten-1-yl-3-anilide.
 3. The compound of claim 1, which is O-(aminosulfonyl)-glycolic acid-N-buten-1-yl-3-anilide.
 4. The compound of claim 1, which is O-(methylaminosulfonyl)-glycolic acid-N-buten-1-yl-3-anilide.
 5. The compound of claim 1, which is O-(ethylaminosulfonyl)-glycolic acid-N-buten-1-yl-3-anilide.
 6. The compound of claim 1, which is O-(propylaminosulfonyl)-glycolic acid-N-buten-1-yl-3-anilide. 